Ether and thioether containing thiolesters

ABSTRACT

New compounds of the formula   WHEREIN R1 represents C1-C14-alkyl, R2 represents methyl or ethyl, Y represents O, -CH2-, C O or S, and one of the radicals Z or W stands for oxygen, while the other represents sulphur, ARE DISCLOSED, A PROCESS FOR THEIR PREPARATION AND A METHOD FOR COMBATING PESTS BY APPLYING THE COMPOUNDS TO THE SAID PESTS.

llnite ttes Karrer et a].

atent l 1 1 [451 Aug. 19, 1975 [54] ETHER AND THIOETHER CONTAINING THEOLESTERS [73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: Nov. 6, 1974 [21] Appl, No.: 521,314

[30] Foreign Application Priority Data Nov. 9. 1973 Switzerland 15812/73 Nov. 9, 1973 Swit7.erland i. [5813/73 Oct. 9. 1974 Switzerland 13565/74 [52] US. Cl 260/455 R; 260/470; 424/301; 424/308 [51] Int. Cl. C07C 157/07 [58] Field of Search 260/455 R [56} References Cited UNITED STATES PATENTS 1733.288 5/1973 Koshigaya et al 260/455 C 3,829,489 8/1974 Edamura et al 260/455 R Primary L'.\'amim'rElbert L. Roberts Assistant Ii.\amiI1erD. R. Phillips Attorney, Agent, or F irmFrederick H. Rabin 57 ABSTRACT New compounds of the formula Y 0 I! Q @-z c-w- (1) wherein R represents C,C ,-alkyl, R represents methyl or ethyl, Y represents 0, CH C=O or S, and one of the radicals Z or W stands for oxygen, while the other represents sulphur,

are disclosed, a process for their preparation and a method for combating pests by applying the compounds to the said pests.

8 Claims, N0 Drawings ETHER AND THIOETHER CONTAINING THIOLESTERS The present invention relates to compounds of the formula wherein R, represents C C -alkyl, R represents methyl or ethyl, Y represents 0, CH C=O or S, and one of the radicals Z or W stands for oxygen, while the other represents sulphur, I Compounds of formula I preferred by virtue of their action are those wherein R represents methyl, ethyl or isopropyl, R represents methyl, Y represents O, CH-;, C=O or S, and one of the radicals Compounds of formula I are produced in a manner known per se by, for example, the following reactions:

(Ill) II (V) (VIII) In formulae II to X, the symbols R R Y, Z and W have the meanings given for formula I, and R stands for alkyl, M for a metal, preferably an alkali metal, and X for halogen, preferably for chlorine or bromine.

The processes A to D are performed at normal pressure. For the obtainment in process D of a higher rate of reaction, it is also possible to use increased pressure and elevated temperature.

The reaction temperatures, which are not very critical, are in most cases between 10 and 140C; the reaction is often performed at the boiling point of the applied solvent, preferably at 0 to 70C.

Suitable solvents for the aforementioned processes are as follows:

Process A: inert solvents, for example: ketones such as acetone, methyl ethyl ketone, cyclohexanone, also dimethylsulphoxide, dimethylformamide and dimethoxyethane.

Process B: for example, others such as tetrahydrofuran, dimethoxyethane, dioxane, also hexamethylphosphonic acid triamide or dimethylformamide, 0p-

tionally in admixture with the above-mentioned ethers.

Process C: inert solvents, particularly hydrocarbons such as benzene, toluene, xylene and hexane.

Process D: for example: hexamethylphosphoric acid triamide, dimethylformamide, and others; it is however also possible to operate without solvents or diluents.

Suitable bases for Process A are, e.g. anhydrous alkali carbonates, alkali alkoxides or alkali hydrides. Bases suitable in the case of Process B are, for example, alkali metal hydrides, alkaline-earth metal hydrides, alkali metal hydroxides and alkali metal alkoxides. And preferred bases for Process C are organic bases, such as trialkylamines or pyridine.

Starting materials of formulae II, III, IV, V, VI and VII are known; thus, for example, the compounds of formula II] can be prepared by the process described in J. Org. Chem. 24, 434 (1959).

In the preparation of compounds of formula I by the aformentioned processes, the two possible geometric isomers can be formed in reciprocal proportions. The described compounds constitute in some cases mixtures of the cisand trans-isomers.

Pure isomers can be obtained, e.g. by application of starting products of uniform configuration in the synthesis of the active substances of formula I, or by fractional distillation, or gasor adsorption chromatographical separation processes from the mixture of cisand trans-isomers.

In the preparation of compounds of formula I, there can be formed in the above-mentioned Process(B), in which in the final stage of synthesis (WITTIG- HORNER reaction) a double bond is formed in the A -position of the side chain, the two geometrical isomers (cis/trans-isomers).

In Processes (A), (C) and (D), the proportions of the geometrical isomers (double bond in the 2,3-position) are given by the applied starting and intermediate products III, VI or VIII, and do not change during synthesis.

The compounds of formula I in which finally there exists a double bond in the 3,4-position of the side chain (vinyl ether) can be prepared by transformation of the compounds having a double bond in the 2,3- position by isomerisation. By migration of the double bond from the 2,3-position to the 3,4-position, there are obtained from (primarily formed) allyl ethers of formula I vinyl ethers of formula I. The preparation of such vinyl ethers is described in Example 2 (see page 14), and is effected, for example, from an allylic ether I primarily formed by a WHITIIG-I-IORNER reaction, under the reaction conditions given therein.

The geometrical isomers of allylic ethers of formula I having a double bond in the 2,3-position can be easily separated by chromatographical separation processes into cisand trans-isomers, whereas this was not possible to attain in the case of the geometrical isomers of the vinylic ethers of formula I (with double bond in the 3,4-position).

The presence of an isomer mixture and its proportions of cisand trans-isomers in vinyl ethers of formula I can however be clearly established by proton resonance spectroscopy.

The compounds of formula I can be used as cis/trans isomer mixtures or as pure isomers for the control of insects. The said compounds are suitable for the control of insects of the families: Tettigonidae, Gryllidae,

Gryllotalpidae, Blattidae, Rcduviidae, Phyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae,

Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymatriidae, Pyrallidae, Culici dae, Tipulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae.

The insecticidal action can be appreciably broadened and adapted to suit given circumstances by the addition of known insecticides and/or acaricides as 'well as insect bait. Suitable additives are, e.g.: organic phosphorus compounds, derivatives of nitrophenols, formamidines, ureas, carbamates and chlorinated hydrocarbons.

The compounds of formula I can be used on their own or together with suitable carriers and/or additives. Suitable carriers and additives may be solid or liquid, and they correspond to the substances common in formulation practice, such as, for example, natural or regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders and/or fertilisers.

For application, the compounds of formula I can be processed into the form of dusts, emulsion concentrates, granulates, dispersions, sprays or solutions, the formulation of these preparations being effected in a manner commonly known in practice.

The agents according to the invention are prepared in a manner known per se by the intimate mixing and- /or grinding of active substances of formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active substances can be obtained and used in the following forms:

Solid preparations:

Dusts, scattering agents, granulates, coated granulates, impregnated granulates and homogeneous granulates;

Liquid preparations:

a. water-dispersible active-substance concentrates:

wettable powders, pastes or emulsions;

b. solutions.

The content of active substance in the above described agents is generally between 0.] and it is mentioned in this connection that in the case of application from an aeroplane, or by means of other suitable application devices, concentrations of up to 99.5%, or even the pure substance, can be employed.

The active substances of formula I can be formulated, for example, as follows:

Dusts:

The following substances are used in the preparation of (a) a 5% dust, and (b) a 2% dust:

a. 5 parts of active substance, 95 parts of talcum;

b. 2 parts of active substance, 1 part of highly dispersed silicic acid, 97 parts of talcum.

The active substances are mixed and ground with the carriers.

Granulate:

The following substances are used to prepare a 5% granulate:

5 parts of active substance,

0.25 part of epichlorohydrin,

0.25 part of cetyl polyglycol ether,

3.50 parts of polyethylene glycol,

91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The

solution thus obtained is sprayed onto kaolin, and the acetone is subsequently evaporated off in vacuo.

Wettable powder:

The following constituents are used for the preparation of (a) a 40%, (b) and (c) a 25%, and (d) a wettable powder:

a. 40 parts of active substance, 5 parts of sodium lig nin sulphonate, 1 part of sodium dibutylnaphthalene sulphonate, 54 parts of silicic acid;

b. 25 parts of active substance, 4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk- /hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, 28.1 parts of kaolin;

c. 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture 1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, 46 parts of kaolin;

d. 10 parts of active substance, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, 5 parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with the additives, and the mixture is then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.

Emulsifiable concentrates:

The following substances are used to prepare (a) a 10% and (b) a 25% emulsifiable concentrate:

a. 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, 3.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium' salt, 40 parts of dimethylformamide, 43.2 parts of xylene;

b. 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, 10 parts of alkylarysulphonate/fatty alcohol polyglycol ether mixture, 5 parts of dimethylformamide, 57.5 parts of xylene.

From these concentrates it is possible to prepare, by dilution with water, emulsions of any desired concentration.

Spray:

The following constituents are used to prepare a 5% spray:

5 parts of active substance,

1 part of epichlorhydrin,

94 parts of ligroin (boiling limits 160190C).

EXAMPLE 1 Preparation of 4-[(4phenoxy)-phenoxy]-3-methyl-2-cis/transbutenic acid-thioethyl ester (cis/trans mixture) and separation of the geometrical isomers (compound with double bond in 2,3-position of the side chain) 3.2 g of sodium hydride dispersion in mineral oil (about 60% NaH) is repeatedly washed with hexane and tetrahydrofuran, and then covered with 100 ml of pure tetrahydrofuran. To this suspension under an N protective gas atmosphere there is added dropwise at 0C within about 30 minutes, with stirring, 21.1 g of diethylphosphoneacetic acid-thioethyl ester (B.P. ll5-118C/0.15 Torr). After a further 30 minutes -of the solution of 19.3 g of 1-(4-phenoxy)-phenoxy-2- propanone in 100 ml of tetrahydrofuran, with the temperature being held at 10C by slight cooling. After fur ther stirring for 1 hour at this temperature, the reaction mixture is poured into ice water, and repeatedly extracted with diethyl ether. The combined organic phases are repeatedly washed with saturated sodium chloride solution and dried by means of sodium sulphate, and the solvent is completely removed in vacuo. For further purification and isomer separation, the oily residue is chromatographed on silica gel (eluant: diethyl ether/hexane 1.4), whereupon pure 4-[(4-phenoxy)- phenoxy]-3-methyl2-cis-butenic acid-thioethyl ester 1.5862) and pure 4-[(4-phenoxy)-phenoxy]-3- methyl-2-transbutenic acid-thioethyl ester (n,, 1.5923) are obtained.

(NMR-spectrum of the cis-compound (CDCl /lOO Mc/ S-values in ppm):

1.23 (triplet/3H), 1.96 (doublet/3H), 2.88 (quartet/2H), 5.10 (singlet, broad/2H), 6.08 (multiplet/IH), 6.78-7.32 (multiplet/9l-l).

NMR-spectrum of the trans-compound (CDSl /1O0 Mc/ S-values in ppm):

1.23 (triplet/3H), 2.13 (singlet/3H), 2.88 (quartet/2H), 4.40 (singlet, broad/2H), 6.3 (multiplet/lH), 6.77-7.31 (multiplet/9H).

EXAMPLE 2 Preparation of 4-[ 4-phenoxy )-phenoxy -3-methyl-3 cis/transbutenic acid-thioethyl ester (compound with rearranged doublebond, i.e. double bond in A 3.2 g of sodium hydride dispersion in mineral oil (about 60% NaH) is repeatedly washed with hexane and tetrahydrofuran, and then covered with 50 ml of tetrahydrofuran and 35 ml of dimethylformamide. To this suspension present under an N -protective gas atmosphere there is added dropwise at about 10C in the course of about 30 minutes, with stirring, 21.1 g of diethylphosphoneacetic acid-thioethyl ester. After a further 30 minutes stirring at 10C, the reaction mixstirring at about 10C, a dropwise addition is made to the reaction mixture, in the course of about 30 minutes,

ture is cooled to 0C; and the solution of 19.3 g of 1-(4- phenoxy)-phenoxy-2-propanone, dissolved in 35 ml of dimethylformamide, is then added dropwise to the reaction mixture; the whole is subsequently heated to room temperature and stirred for a further 20 hours at room temperature. For further processing, the contents of the flask are poured into ice water, and repeatedly extracted with diethyl ether. The combined organic phases are repeatedly washed with saturated sodium chloride solution and dried by means of sodium sulphate, and the solvent is removed in vacuo. For further purification, the oily residue is chromatographed through silica gel (eluant: diethyl ether/hexane 1:4), whereupon the pure isomer mixture of 4-[(4-phenoxy)- phenoxy]3-methyl -3-cis/trans-butenic acid-thioethyl ester (isomer ratio about 45:51 n 1.5774) is obtained. The geometrical isomers cannot be separated from each other by layeror column-chromatography.

NMR-spectrum of the chromatographically purified cis/trans-isomer mixture (CDSl Mc/ B-values in ppm.):

1.22 and 1.24 (each 1 triplet/together 3H), 1.74 and 1.78 (each 1 doublet/together 3H), 2.87 and 2.89 (each 1 quartet/together 2H), 3.18 and. 3.43 (each 1 singlet/together 2H), 6.37 (broad/1H), 6.90-7.36 (multiplet/9H).

The following compounds are obtained in an analogous manner:

CH. trans compound 5 cis compound trans compound (I ClS compound CH trans compound CH cis compound trans Compound CH3 CIS compound CH3 trans compound C 1. ClS compound .1 trans compound cis/trans compound cis/trans compound CH cis/trans compound cis compound cis/trans compound EXAMPLE 3 Contact action on Dysdercus-fasciatus larvae A specific amount of a 0.1% acetonic active substance solution (corresponding to 10 mg of active substance per square metre) was transferred by pipet to an aluminium dish and uniformly distributed. After evaporation of the acetone, 10 larvae in the 5th stage of Dysdercus fasciatus were placed into the treated dish containing feed and moist cotton wool. The dish was then covered with a perforated lid. After about days, i.e. as soon as the control insects had moulted into adults, the test insects were examined to determine the number of normal adults.

Compounds according to Examples 1 and 2 exhibited a good action in the above test.

EXAMPLE 4 Contact action on Aedes-aegypti larvae About two-day-old larvae of the yellow-fever mos- EXAMPLE 5 Contact action on Tenebrio-molitor pupae A specific amount of a 0.1% acetonic active substance solution corresponding to 10 mg of active substance per square metre was transferred by pipet into an aluminium dish and uniformly distributed. After evaporation of the acetone, 10 freshly formed pupae were placed on the treated surface, and the dish was covered with a perforated lid. After the control insects had left the cocoon as imagines, the test insects were examined to determine the number of normal adults.

1 l l 2 Compounds according to Examples 1 and 2 exhibited R1 ep esents methy ethyl r isopropyl, a good action in the above test 2 represents y What we claim is: Y represents 0, CH C=O or S, and one of the 1. Compounds of the formula radicals Z is oxygen or sulfur and W is sulfur.

3. 4-[4-( Phenoxy)-phenoxy]-3-methyl-2-transbutenic acid-thioethyl ester according to claim 2.

Y 4. 4-[4-(Phenoxy)-phenoxy]-3-methyl-3 -cis/trans- Z *AC-W-R butenic acid-thioethyl ester according to claim 2.

5. 4-[4-(Phenoxy)-phenoxyl-3-methyl-2-cis/trans- R2 butenic acid-thioisopropyl ester according to claim 2.

(I) 6. 4-(Benzyl-phenoxy)-3-methyl-2-cis/trans-butenic acid-thioethyl ester according to claim 2. wherein 7. 4-(benzyl-phenoxy)-3-methyl-Z-cis/trans-butenic R represents C C -alkyl, acid-thioisopropyl ester according to claim 2. R represents methyl or ethyl, 8. 4-[(4-Phenylthio)-phenoxy]-3-methyl-2-trans- Y represents 0, CH C=O or S, and one of the butenic acid-thioisopropyl ester according to claim 2.

radicals Z is oxygen or sulfur and W is sulfur. 2. Compounds according to claim 1, wherein 

1. COMPOUNDS OF THE FORMULA
 2. Compounds according to claim 1, wherein R1 represents methyl, ethyl or isopropyl, R2 represents methyl, Y represents O, -CH2-, >C O Or S, and one of the radicals Z is oxygen or sulfur and W is sulfur.
 3. 4-(4-(Phenoxy)-phenoxy)-3-methyl-2-trans-butenic acid-thioethyl ester according to claim
 2. 4. 4-(4-(Phenoxy)-phenoxy)-3-methyl-3-cis/trans-butenic acid-thioethyl ester according to claim
 2. 5. 4-(4-(Phenoxy)-phenoxy)-3-methyl-2-cis/trans-butenic acid-thioisopropyl ester according to claim
 2. 6. 4-(Benzyl-phenoxy)-3-methyl-2-cis/trans-butenic acid-thioethyl ester according to claim
 2. 7. 4-(benzyl-phenoxy)-3-methyl-2-cis/trans-butenic acid-thioisopropyl ester according to claim
 2. 8. 4-((4-Phenylthio)-phenoxy)-3-methyl-2-trans-butenic acid-thioisopropyl ester according to claim
 2. 